Electrolytic device



Patented Apr. 28, 1942 UNITED STATES I PATENT OFFICE ELECTROLYTIC navroa Joseph B. Brennan, Euclid, Ohio Application August 9, 1931, Serial No. 158,105 (01. 175-315 30 Claims.

This invention relates to electrolytic devices, and more particularly to electrodes for electrolytic devices such as electrolytic condensers, rectifiers, lightning arresters and the like. This application is a continuation in part of my copending application Serial No. 662,107, filed March 22, 1933 now Patent No. 2,104,018. In this application the invention is described particularly with reference to electrolytic condensers, but it is to be understood that themvention may be applied to various other typesof electrolytic devices.

It is among the general objects of my invention to provide electrolytic devices such as electrolytic condensers, and electrodes therefor, which can be manufactured economically and rapidly and which will operate efllciency over long periods of time with low resistance and power factor losses. It'is also among the objects of my invention to provide electrodes for electrolytic devices which will have an efiective area in contact with the electrolyte many times the plane area thereof. Another object is to provide electrodes which, when provided with dielectric films and incorporated in electrolytic condensers, will have capacities many times greater than capacities of plane surfaced electrodes of similar size. Another object is to provide an electrode comprising a strip having a porous or permeable surface, the strip being flexible so that it can be bent into various forms.

Briefly, I obtain the advantages noted above and economically produced efiicient electrodes for electrolytic devices by spraying molten metal such as finely divided aluminum of high purity upon a base which preferably consists of a thin, flexible strip of porous or woven material. As described in my copending application noted above, the sprayed deposit consists in a very large number of minute metallic particles which adhere to the base and cohere to each other to produce a thin porous layer that is conductive throughout substantially its layer deposited ona base which is also porous or permeable produceslan electrode which is porous or reticulated throughout so that in use the surface area of the metallic particles exposed directly to the electrolyte is very large,

resulting in a compact electrode which, when provided with a dielectric film, capacity per unit of plane area.

because of the very large area of metallic particles in contact with the electrolyte and because .of the porous structure of the electrode,

has a high the current densities may be keptat a low value,

entire area. Such a resistance is reduced and long life and efficient operation of electrolytic devices embodying my invention is thus insured.

Various metals may be deposited on suitable bases. depending upon the service for which the electrode is intended. For example, in the production of filmed electrodes for electrolytic con-' densers, I preferably spray finely divided molten particles of high purity aluminum on strips of flexible porous material. The spraying operation may be carried out with well known apparatus in the manner described in greater detail in my copending application referred to above to produce a thin, porous or permeable deposit of finely divided aluminum particles which adhere to the base material and cohere to each other to produce a layer which is conductive throughout substantially its entire area, and which has a very large effective area. Various porous or woven materials may be used advantageously. For example, I may spray aluminum on a woven screen composed of fine aluminum wires, upon a soft permeable base made of paper such as ordinary filter paper, upon cloth woven of textile materials such as the gauze used in the manufacture of spacers for electrolytic condensers, or upon cloth woven of glass threads or filaments.

The molten metallic particles are preferably sprayed on both sides of the base, a fine spray being employed. Preferably thin layers are deposited in order to save material, it only being necessary to spray a sufilcient thickness to in-' sure that the sprayed layers will be conductive throughout substantially their entire areas. In

- the case of aluminum anodes, for example, ex-

cellent resultsmay be obtainer by spraying layers about 1 to 3 thousandths of an inch thick. While the sprayed material does have the eflect of stiffening the base material to some extent, the completed electrodes retain suflicient flexibility so that they can be readily bent into desired shapes. When such electrodes, suitably provided with dielectric films, are incorporated in electrolytic condensers, capacities as much as ten or more times the capacity of condensers embodying ordinary aluminum electrodes of the Furthermore,

same plane area may be obtained. Furthermore, by the use of such electrodes condensers having extremely low resistance and in which the power factor losses are less than 4 per cent may be produced. In spraying themetal on flexible porous strips of the types mentioned above, I

preferably carry out the operation in a continuous manner, thus producing continuous strips of material suitable for use as electrodes. If the electrodes are intended for use as anodes in electrolytic condensers, the sprayed strips may convem'ently be formed with a dielectric film by continuously passing them through a suitable film forming bath and applying the necessary voltages to the strips. Thereafter the strips may be cut into pieces of the desired length, bent into the proper shape if necessary, and incorporated in condensers.

Further advantageous features and other objects of my invention will be evident to those skilled in the art from the following description of preferred forms thereof, reference being made to .the accompanying drawing in which Figure l is a plan view of an electrode made according to my invention; Figure 2 is a section through the electrode of Figure 1 as indicated by the line 2-2; Figure 3 is a view of a paste type electro lytic condenser made according to my invention; Figure 4 is a sectional view of a wet type electrolytic condenser made according to my invention; Figure 5 is a section as indicated by the line 5--5 on Figure 4; and Figures 6, 7 and 8 illustrate different steps in a preferred method of making electrodes according to my invention.

A illustrated somewhat diagrammatically in Figures 1 and 2, the base or backing material of an electrode made according to my invention preferably comprises a porous flexible strip l illustrated herein as being of woven material. Any suitable strands or filaments may b employed in weaving the strip, it only being necessary to select filaments which will not react with or contaminate the electrolyte to be employed in the condenser or other electrolytic device and which will not otherwise adversely affect the operation of the device. In connection with electrolytic condensers, I prefer that the cloth be woven of materials such as purified cotton threads or yarns, spun glass filaments or fine metallic wires, the wires employed being of the same material as the metal to be sprayed thereon. One or more thicknesses of material may be employed, depending on the desired thickness of the electrode which is to be produced. When multiple layers of cloth are employed, thesprayed metal bonds the layers together.

The strip I0 is provided with areas of sprayed metal IS on either side thereof. Preferably the sprayed metal is only 0.001 inch to 0.003 inch in thickness, the thickness of th layers being greatly exaggerated throughout the drawing. The spraying of such thickness of metal, particularly when a gauze base is employed, results in an electrode that is sufficiently open mesh and porous to permit light to pass through the electrode layer at a multiplicity of points distributed throughout its area. The sprayed areas may be stopped short of the edges of th strip, particularly when a non-conductive material such as cotton cloth or glass cloth is employed, so as to provide insulating edges for the electrodes. The layers l as previously noted comprise a very large number of finely divided cohering metallic particles, the layers being conductive throughout substantially their entire area.

It the electrode is intended for use as an anode in an electrolytic condenser, the layers l5 are formed of aluminum or other film forming metal,

. and after the spraying operation has been completed the electrodes may be provided with dielectric films by subjecting them to electrolysis in a. film forming bath such as a solution of borax and boric acid. The composition of the bath, the temperature of the bath and the voltage applied to the electrodes all may be controlled in ways well known to those skilled in the art and depending upon the particular servicefor which the electrode is intended. Various methods of forming dielectric films are well known in the art. Such methods, perse, form no part of the present invention and therefore will not be discussed further herein. For the purposes of this application, it is suflicient to state that the dielectric film conforms substantially to the contour of the many minute particles and thus the area of the film is greatly increased as compared to the plane area of the electrode.

When such an electrode is incorporated in an electrolytic cell, the electrolyte permeates the sprayed metallic layers as well as the porous base material. Thus the effective area of the electrode will be many times the plane area thereof. It will be evident that condensers embodying such electrodes will have very large capacities per unit of plane area, since the capacity of a condenser is a function of the area of the plates and in my device the area of the plate consists in the sum of the exposed areas of all of the many minute cohering metallic particles.

Electrodes made according to my invention may be incorporated in various types of electrolytic devices. In Figure 3, for example, I have illustrated a paste type condenser embodying my electrodes. As illustrated in the drawing, such a condenser, when intended for use in direct current circuits, may comprise a plurality of anodes "5 which may be made in the manner described above, and a plurality of cathodes H. The cathodes may be similar to the anode plates except that in the case of condensers intended for direct current service, the cathodes need not be provided with dielectric films. Or, if desired,the cathodes may be made of ordinary metallic sheets or may be made of sprayed metals which will not become filmed, such a copper. In condensers intended for alternating current service, both sets of electrodes are preferably provided with dielectric films. The anodes and cathodes are provided with suitable terminals such as strips of metallic foil l8 and I9, respectively, and the electrodes may be prevented from coming in contact with each other by suitable porous separators such as the paper strips 20. The whole condenser assembly may be suitablyimpregnated with a pasty or viscous electrolyte such as that described in my copending application Serial No. 759,433, filed Dec. 27, 1934, and may be enclosed in a suitable container orcasing in a manner known to those skilled in the art.

As illustrated in Figures 4 and 5, electrodes made according to my invention may be conveniently incorporated in electrolytic condensers of the wet or liquid type. Such a condenser may comprise a can 25 which serves as the cathode of the condenser and also as a container for the electrolyte. The can has a depending hollow neck portion 26 and is provided with a closure member 21. The electrode 28 which constitutes the anode of the condenser may be suitably supported within the container and is immersed in the electrolyte. r

I Preferably the anode 28 is constructed as illustrated in Figure 6 of the-drawing in such a manner as to eliminate the need for any mechanical support for the anode within the container and also to eliminate the necessity for providing a separate insulating spacer between. the anode and the container. Thus, the anode 28 preferably comprises a backing of woven non-conductive material 29 such as cotton or glass cloth having sprayed areas 30 on either side thereoi. The sprayed areas are spaced from the top and bottom edges of the strip 29 leaving unsprayed nonconductive areas 3| and 32, and there is a con- Eiderably unsprayed area. 33 at one end oi the ectrode- This electrode can very readily be incorporated in a condenser of the type illustrated in Figures 4 and 5 by merely coiling the flexible electrode into the form of a spiral with the unsprayed portion 33 forming the outer end of the spiral. The portion 33 is oi sufllcient length to extend at least once around the spiral electrode to thus provide an insulating spacer.

integral with the electrode and surrounding the sprayed areas 39. The spiral electrode is inserted into the can or container with the unsprayed area 33 in engagement with the inside of the can and the unsprayed lower edge portion 3! in engagement with the bottom portion 39 of the can, the upper unsprayed edge 32 holding the electrode against upward movement by engaging, for example, the inwardly deformed portion 35 of the container.

' By this construction, the metallic sprayed areas of the electrode are securely and definitely spaced away from the container and closure member by the non-conductive edge portions of the backing member 29 and the entire electrode is mechanically supported within the container so' that no further mechanical support is necessary. Thus the usual rod or riser may be eliminated and the electrical contact between an.ex-

terior circuit and the electrode may be made by a lead-in, shown herein as a wire 36, which extends downwardly through the neck portion 26. Preferably the lead-in 36 extends through a rubber grommet member 31, and the neck portion is deformed inwardly as at 38 to compress the rubber grommet member and seal the neck portion and lead-in wire 36 against leakage of fluid.

To provide an efiective and economical connection between the lead-in 38 and the sprayed areas of the electrode, the lead-in is preferably extended'along the backing material as indicated at 39 in Figure 6. The wire or other conductor may be secured to the backing material by stitching or may be merely laid along the strip before the spraying operation takes place. By this sequence of operation, eflective contact between the conductor and the sprayed material is assured, and the sprayed material secures the conductor to the base strip. Electrodes of this type, that it with an additional conducting member incorporated therein, may obviously be advantageously used in connection with the dry type of condenser heretofore described. Such electrodes have extremely low resistance because of the fact that the conducting members extend throughout the length of the electrode.

In Figures '7 and 8, I have illustrated steps of a method which may be conveniently employed in the manufacture of electrodes of the general type illustrated in Figure 6. As shown in Figure 7, the first step preferably is to provide the strip of woven backing material 29 with a conducting member such as the stitched wires 39 extending with the stitching 39 therein is then provided with the sprayed areas 30 as indicated in Figure 8. The spraying operationmay be carried out continuously, the strip being spraye'dsimultaneously from both sides. Metallic shield members may be employed to prevent the molten metal from adhering to the portions 3|, 32 and 33, or, if desired, to cause the sprayed material to be deposited in any desired patterns.

The spraying operation thus produces a strip oi backing material having spaced sprayed areas thereon, the entire strip being conductive throughout its length by reason of the conductors 39. The conductive strip may then be passed through a forming bath in a continuous manner so that as each portion of the strip leaves the bath it will be properly formed with a dielectric film. Thereafter the strip may be cut in the spaces between the successive sprayed areas and the wire stitching ripped out from such spaces to provide the electrode illustrated m Figure 6. This electrode is then bent into a spiral or other convenient shape and may be incorporated into a condenser as described above.

Various changes and modifications in my invention will be evident to those skilled in the art. Obviously my inventiorrmay be applied to various types oi electrolytic devices and various changes can be made as to both the articles and methods disclosed herein without departing from the spirit and scope oi my invention. It is therefore to be understood that my patent is not limited to the preferred form of myinvention disclosed herein or in any manner other than by the scope of the appended claims when given the range of equivalents to which my patent may be entitled.

I claim:

1. An electrolytic condenser comprising a plurality of plates, each plate comprising a flexible porous base having a layer of ,minute cohering particles or metal deposited thereon and adhering thereto, insulating means for spacing said plates apart, and electrolyte permeating said bases and said layers and means for connecting said plates to an external circuit.

2. An electrolytic condenser comprising a plurality of plates, at least one of said plates comprising a flexible porous basehaving a layer of minute cohering particles of film forming metal deposited thereon and adhering thereto, an electrolvte permeating said base and said layer and means for connecting said plates to an external circuit.

3. An electrolytic condenser comprising a plurality of plates, at least one of said plates comprising a flexible porous base of insulating material having a layer of minute cohering particles of fllm forming metal deposited thereon and adhering thereto, an electrolyte permeating said base and said layer and means for connecting said plates to an external circuit.

4. An electrolytic condenser comprising a container for electrolyte, a film forming electrolyte within said container, an electrode immersed in said electrolyte and comprising a strip of flexible porous insulating material having a portion of the area thereof coated with a conductive layer of finely divided particles of film forming material, said electrode being wound into spiral form in such manner that the uncoated areas of the insulating material prevent contact between the layer of film forming material and the container,

and a lead-in wire extending from the layer of film forming material to the exterior of the container and insulated from the exterior of the container.

5. An electrolytic condenser comprising a container for electrohrte-formedof conductive material, electrolyte within said container, anelectrode immersed in said electrolyte and comprising a base of flexible' porous insulating material having a portion of the area thereof coated with a conductive layer of finely divided metallic particles, another portion of the area being uncoated, saidelectrode being disposed within said container in such manner that theuncoated area of the base prevents contact between the conductive layer of metallic particles and the container.

6. An electrolytic condenser comprising a container for electrolyte, a film forming electrolyte within said, container, an electrode immersed in said electrolyte and comprising a strip of flexible orous insulating material having a portion of the area thereof coated with a conductive layer of finely divided particles of film forming material, another portion of the area being uncoated, said electrode being disposed within said container in such manner that the uncoated area of the insulating material prevents contact between the layer of film forming material and the container.

'7. A dry electrolytic condenser electrode terminal assembly comprising an electrode formed of a sheet of perforate material having a spraydeposit of film-forming metal thereon and a metal terminal member electrically and mechanically bonded to said electrode by said spraydeposit. a

8. A dry electrolytic condenser electrode-terminal assembly comprising an electrode formed of at least one sheet of cloth having a spraydeposit of film-forming metal thereon and a metal terminal tab for said electrode electrically and mechanically connected thereto by adhesion of said spray deposit to said terminal.

9. An electrode for electrolytic devices comprising a sheet of porous insulating material having a spray deposit of metal thereon and a metallic conductor extending along said sheet throughout substantially the entire length of said spray deposit, said conductor making electrical contact with said spray deposit and being secured to said porous material by said spray deposit.

10. An electrode for electrolytic devices comprising a sheet of insulating material having a spray deposit of metal thereon and a metallic whergby the resistance of said electrode is reduce 14. An electrode for electrolytic condensers comprising a flexible woven base having a metallic conductor extending therealong, and a spray deposited layer of film forming metal adhering to said base and making electrical contact with said conductor, whereby the resistance of said electrode is reduced.

15. In an electrolytic device, an electrode comprising a base of flexible porous material having a conductive layer of minute metallic particles deposited thereon, and an electrolyte permeating said base and said layer.

16. In an electrolytic device, an electrode comprising a gauze base having a conductive layer of minute metallic particles deposited thereon, and an electrolyte permeating said base and said layer.

1'7. In an electrolytic device, an electrode comprising a porous flexible base of insulating material having a conductive layer of finely divided metallic particles deposited thereon and adhering thereto, and an electrolyte permeating said base and said layer.

18. In an electrolytic device, an electrode comprising a porous flexible base of woven glass cloth and said layer.

19. In an electrolytic device, an electrode comprising a flexible porous base having a reticulated porous surface composed of minute cohering particles of film forming material, a dielectric film formed on the surfaces of the particles and conforming thereto, and an electrolyte permeatconductor extending along said sheet, said conductor making electrical contact with said spray deposit and being secured to said insulating material by said spray deposit.

11. An electrode for electrolytic condensers comprising-a sheet of porous insulating material having a spray deposit of film forming metal thereon and a metallic conductor extending along said sheet, said conductor making electrical contactwith said spray deposit, and being secured to said porous material by said spray deposit.

12. An electrode for electrolytic devices com prising a base of non-conducting material having a metallic conductor extending therealong and a sprayvdeposited metallic layer adhering to said base and overlying and making electrical contact with said conductor, whereby the resistance of said electrode is reduced.

13. An electrode for electrolytic devices comprising a porous flexible base having a metallic conductor extending therealong and a spray deposited metallic layer adhering to said base and making electrical contact with said conductor,

20. In an electrolytic device, an electrode comprising a woven fabric base having a reticulated porous surface composed of minute cohering particles of film forming material, a dielectric film formed on the surfaces of the particles and conforming thereto, and an electrolyte permeating said base and said surface.

21. In an electrolytic device, an electrode comprising a woven strip of insulating material having a reticulated porous surface composed of minute cohering particles of film forming material, a dielectric film formed on the surfaces of the particles and conforming thereto, and an electrolyte permeating said base and said surface.

22. In an electrolytic device, an electrode comprising a. flexible porous base of insulating material having a portion of the area thereof coated with a conductive layer of finely divided metallic particles, said conductive layer being spaced from the edges of the base, and an electrolyte per meating said base and said surface. r

23. In an electrolytic device, an electrode com prising a flexible porous base of woven glass cloth having a portion of the area thereof coated with a conductive layer of finely divided metallic particles, said conductive layer being spaced from the edges of the base material, and an electrolyte permeating said base and said surface.

24. In an electrolytic device, an electrode comprising a flexible porous base having a portion of the area thereof coated with a conductive layer of finely divided particles of film forming material, said conductive layer being spaced from the edges of the base material, and an electrolyte permeating said base and said surface.

26. A dry electrolytic condenser comprising vtwo electrodes, a spacer and an electrolyte, one

of said electrodes comprising a cloth base and finely divided film-forming Y metal deposited thereon, said electrode having recesses in the surface thereof resulting from the contours and lattice structure of said cloth base, said metal particles cohering to provide a conductive path along the electrode layer and said electrode being sumciently open-mesh and porous to permit light to pass through the electrode layer at a multiplicity of distributed points throughout its area.

27. A dry electrolytic condenser comprising two electrodes and paper spacers in enrolled form impregnated with a viscous film forming electrolyte, one of said electrodes comprising a cloth base and finely-divided film-forming metal deposited thereon, said electrode having recesses in the surface thereof resulting from the contours and lattice structure of said cloth base, said meta1 particles cohering to provide a conductive path along the electrode layer and said electrode being sufilciently open-mesh and porous to permit light to pass through the electrode layer at a multiplicity of distributed points throughout its area.

28. A flexible sheet electrode for dry electrolytic condensers comprising a cloth base and finely divided aluminum deposited thereon, said electrode having recesses in thesurface thereof resulting from the contours and lattice structure of said cloth base, said metal particles cohering to provide a conductive path along the electrode layer and said electrode being sufilciently openmesh and porous to permit light to pass through the electrode layer at a multiplicity of distributed points throughout'its area.

29. In an electrolytic device an electrode comprising a woven wire mesh having a conductive layer of minute metallic particles deposited thereon the wire mesh and the deposited particles being composed of the same metal, and an electrolyte permeating said base and'said layer.

30.A dry electrolytic condenser electrode terminal assembly comprising an electrode formed of two layers of cloth having a spray deposit of film forming metal thereon and a terminal tab extending beyond an edge of said electrode, said spray deposit bonding said cloth layers and said terminal tab together in a unitary assembly.

JOSEPH B. BRENNAN. 

